ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Polymer–MOF Hybrid Composites with High Porosity and Stability through Surface-Selective Ligand Exchange

Cite this: Chem. Mater. 2018, 30, 23, 8639–8649
Publication Date (Web):November 17, 2018
Copyright © 2018 American Chemical Society

    Article Views





    Other access options
    Supporting Info (2)»


    Abstract Image

    Hybrid materials containing organic polymers and metal–organic frameworks (MOFs) have attracted attention for their potential to harness both diverse functionality and high processability, but their fabrication is challenged by incompatibilities of the parent components. The poor solubility of MOFs hinders uniform dispersion throughout a polymer matrix and may cause aggregation that is not only detrimental to the permeability of substrates, but also limits the structural integrity of the polymer. Meanwhile, polymer chains can block or penetrate the porous structures and compromise MOF functionality by reducing surface area and pore size. We report a versatile method of covalent hybridization through post-synthetic ligand exchange to form a cross-linked polymer–MOF composite. The resulting network structure allows for the formation of robust, monolithic composites with variable MOF loadings that may exceed 80% wherein ligand exchange is limited to surface sites so as to fully preserve MOF surface area and porosity. The synthesis can be performed from a diverse set of inexpensive starting materials, encouraging the design of new functional materials across a wide range of applications.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b03881.

    • Video of composite formation (MPG)

    • PXRD diffractograms of MOF-5, PAA, MOF-5/PAA, and MOF-5/PI; PXRD diffractograms of ZIF-8 and ZIF-8/MOF-5 composites; PXRD diffractograms of UiO-66; 1H NMR spectrum of PAA; 1H NMR spectrum of MEPA; 1H NMR spectrum of PVBA; GPC traces of PAA-high, PAA-low, and MEPA; polymer molecular weight data; SEM images of free polymer-coated MOF-5; FT-IR spectra of PAA and PI; FT-IR spectra of MOF-5/PAA and MOF-5/PI; TGA curves of microcrystalline MOF-5, PAA, and microcrystalline MOF-5/PAA; TGA curves of nanocrystalline MOF-5, PAA, and nanocrystalline MOF-5/PAA; TGA curves of ZIF-8, PAA, and ZIF-8/PAA; DSC curves of PAA, microcrystalline MOF-5/PAA, nanocrystalline MOF-5/PAA, and ZIF-8/PAA; N2 adsorption–desorption isotherms of ZIF-8 and ZIF-8/PAA; and N2 adsorption–desorption isotherms of nanocrystalline MOF-5 and nanocrystalline MOF-5/PAA (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 70 publications.

    1. Meghan G. Sullivan, Heshali K. Welgama, Matthew R. Crawley, Alan E. Friedman, Timothy R. Cook. Phase-Pure Zirconium Metal–Organic Polyhedra Enabled by a Ligand Substitution Strategy. Chemistry of Materials 2024, 36 (1) , 567-574.
    2. Shanshan Xu, Xiangyu Guo, Zhihua Qiao, Chongli Zhong. Facile in Situ Polymer Functionalization Approach for Constructing Water-Resistant Metal–Organic Frameworks. Industrial & Engineering Chemistry Research 2023, 62 (4) , 1899-1905.
    3. Subharanjan Biswas, Mohamed Haouas, Cátia Freitas, Carla Vieira Soares, Abeer Al Mohtar, Ali Saad, Heng Zhao, Georges Mouchaham, Carine Livage, Florent Carn, Nicolas Menguy, Guillaume Maurin, Moises L. Pinto, Nathalie Steunou. Engineering of Metal–Organic Frameworks/Gelatin Hydrogel Composites Mediated by the Coacervation Process for the Capture of Acetic Acid. Chemistry of Materials 2022, 34 (21) , 9760-9774.
    4. Yuzhang Yang, Yunqian Gong, Xingliang Li, Minji Li, Qinping Wei, Beibei Zhou, Junke Zhang. Alkaline-Stable Peroxidase Mimics Based on Biological Metal–Organic Frameworks for Recyclable Scavenging of Hydrogen Peroxide and Detecting Glucose in Apple Fruits. ACS Sustainable Chemistry & Engineering 2022, 10 (32) , 10685-10698.
    5. Xiaoxiao Zheng, Lijuan Shen, Fengcai Lin, Yanlian Xu, Qi Lin, Lilong Jiang. Bimetallic Metal–Organic Frameworks MIL-53(xAl–yFe) as Efficient Catalysts for H2S Selective Oxidation. Inorganic Chemistry 2022, 61 (8) , 3774-3784.
    6. Matthew A. Pearson, Mircea Dincă, Jeremiah A. Johnson. Radical PolyMOFs: A Role for Ligand Dispersity in Enabling Crystallinity. Chemistry of Materials 2021, 33 (24) , 9508-9514.
    7. Chen Gu, Cong Lu, Yu-Xia Gao, Peng Tan, Song-Song Peng, Xiao-Qin Liu, Lin-Bing Sun. Hybridization with Ti3C2Tx MXene: An Effective Approach to Boost the Hydrothermal Stability and Catalytic Performance of Metal–Organic Frameworks. Inorganic Chemistry 2021, 60 (3) , 1380-1387.
    8. Yansong Jiang, Jing Sun, Xiaona Yang, Jieyu Shen, Yu Fu, Yong Fan, Jianing Xu, Li Wang. Cd-MOF@PVDF Mixed-Matrix Membrane with Good Catalytic Activity and Recyclability for the Production of Benzimidazole and Amino Acid Derivatives. Inorganic Chemistry 2021, 60 (3) , 2087-2096.
    9. Liang Feng, Kun-Yu Wang, Gregory S. Day, Matthew R. Ryder, Hong-Cai Zhou. Destruction of Metal–Organic Frameworks: Positive and Negative Aspects of Stability and Lability. Chemical Reviews 2020, 120 (23) , 13087-13133.
    10. Joanna Kaźmierczak, Dariusz Lewandowski, Grzegorz Hreczycho. B(C6F5)3-Catalyzed Dehydrocoupling of POSS Silanols with Hydrosilanes: A Metal-Free Strategy for Effecting Functionalization of Silsesquioxanes. Inorganic Chemistry 2020, 59 (13) , 9206-9214.
    11. Vincent J. Pastore, Timothy R. Cook. Coordination-Driven Self-Assembly in Polymer–Inorganic Hybrid Materials. Chemistry of Materials 2020, 32 (9) , 3680-3700.
    12. Maryam Firoozi, Zahra Rafiee, Kheibar Dashtian. New MOF/COF Hybrid as a Robust Adsorbent for Simultaneous Removal of Auramine O and Rhodamine B Dyes. ACS Omega 2020, 5 (16) , 9420-9428.
    13. Daniel S. Kissel . Integrating Faculty Research into the Undergraduate Chemistry Curriculum: A CURE Using Porous Composite Materials for Water Remediation. 2020, 79-104.
    14. Mohamed E. Mahmoud, Asmaa K. Mohamed, Mohamed F. Amira, Seleim M. Seleim. Novel Nanostructured Metal–Organic Framework-Bonded Silica Amine and Polymer: Facile Synthesis, Kinetics, Isotherms, and Thermodynamics Evaluation for Adsorption of Yttrium(III) Ions. Journal of Chemical & Engineering Data 2019, 64 (12) , 6060-6070.
    15. Francesca Monforte, Mario Urso, Alessandra Alberti, Emanuele Smecca, Salvo Mirabella, Corrado Bongiorno, Giovanni Mannino, Guglielmo Guido Condorelli. New Synthetic Route for the Growth of α-FeOOH/NH2-Mil-101 Films on Copper Foil for High Surface Area Electrodes. ACS Omega 2019, 4 (20) , 18495-18501.
    16. Yuan Zhao, Fangjie Zheng, Lixia Shi, Han Liu, Wei Ke. Autoluminescence-Free Prostate-Specific Antigen Detection by Persistent Luminous Nanorods and Au@Ag@SiO2 Nanoparticles. ACS Applied Materials & Interfaces 2019, 11 (43) , 40669-40676.
    17. Mantas Šimėnas, Sergejus Balčiu̅nas, Adrian Gonzalez-Nelson, Martynas Kinka, Maciej Ptak, Monique A. van der Veen, Mirosław Mączka, Ju̅ras Banys. Preparation and Dielectric Characterization of P(VDF–TrFE) Copolymer-Based Composites Containing Metal–Formate Frameworks. The Journal of Physical Chemistry C 2019, 123 (26) , 16380-16387.
    18. Liang Feng, Xiu-Liang Lv, Tian-Hao Yan, Hong-Cai Zhou. Modular Programming of Hierarchy and Diversity in Multivariate Polymer/Metal–Organic Framework Hybrid Composites. Journal of the American Chemical Society 2019, 141 (26) , 10342-10349.
    19. Fateme Parsapour, Morteza Moradi, Vahid Safarifard, Soheil Sojdeh. Polymer/MOF composites for metal-ion batteries: A mini review. Journal of Energy Storage 2024, 82 , 110487.
    20. Yanfang Fan, Xiya Yuan, Xiangyu Meng, Nanwen Li, Zhiguang Zhang. Sub-T promoted solid-state interfacial linker exchange in ZIF-based hybrid membranes towards enhanced gas-sieving performance. Journal of Membrane Science 2024, 693 , 122372.
    21. Yu-Chuan Hsu, Kun-Yu Wang, Kui Tan, Joshua A. Powell, Hong-Cai Zhou. Diversity Oriented Synthesis of Metal-Organic Frameworks. 2024, 191-211.
    22. Mandla B. Chabalala, Bakang M. Mothudi, Bulelwa Ntsendwana. MOF based nanocomposites for photocatalytic degradation of pollutants in water: A critical review. Journal of Photochemistry and Photobiology A: Chemistry 2024, 447 , 115244.
    23. Leslie B. Reyna Ramirez, Cesar M. Oliva González, Boris I. Kharissov, Lucy T. González, Oxana V. Kharissova, Naveen V. Kulkarni, Igor E. Uflyand. Surface modification of metal-organic frameworks and their applications for the gas adsorption. 2024, 961-986.
    24. B.D.S Deeraj, Jitha S Jayan, Akhila Raman, Aparna Asok, Rhiya Paul, Appukuttan Saritha, Kuruvilla Joseph. A comprehensive review of recent developments in metal-organic framework/polymer composites and their applications. Surfaces and Interfaces 2023, 43 , 103574.
    25. Khaled Dassouki, Sanchari Dasgupta, Eddy Dumas, Nathalie Steunou. Interfacing metal organic frameworks with polymers or carbon-based materials: from simple to hierarchical porous and nanostructured composites. Chemical Science 2023, 14 (45) , 12898-12925.
    26. Renuka Garg, Rana Sabouni, Abdulwahab Alaamer, Aysha Alali, Dana Al-Muqbel, Hind Alqassem, Khawla Almazrooei. Recent development in metal-organic framework-based hybrid nanocomposites for pollutants remediation from wastewater: Challenges and opportunities. Environmental Technology & Innovation 2023, 32 , 103446.
    27. Brij Mohan, Diksha Dhiman, Virender, Mehak, Priyanka, Qiming Sun, Masood Jan, Gurjaspreet Singh, Neera Raghav. Metal-organic frameworks (MOFs) structural properties and electrochemical detection capability for cancer biomarkers. Microchemical Journal 2023, 193 , 108956.
    28. Dudu Li, Ning Li, Wenbin Liu, Shanshan Xu, Yuxiu Sun, Zhihua Qiao, Chongli Zhong. Highly water-stable MOF-74 synthesized by in-situ trace polymer modification. Polymer 2023, 281 , 126112.
    29. Mozhgan Parsaei, Kamran Akhbari, Jonathan White. Synthesis, characterization and comprehensive study of a 3D Co(II) coordination polymer antibacterial activity. Journal of Molecular Structure 2023, 1283 , 135224.
    30. O. Lekshmy, K. S. Beena Kumari, R. Sudha Devi. Ecofriendly Synthesis and Characterization of Magnesium based Metal - Organic Frame Work. Journal of Surface Science and Technology 2023, , 203-209.
    31. Aleksander Ejsmont, Agata Chełmińska, Martyna Kotula, Anita Kubiak, Marcelina Kotschmarów, Aleksandra Galarda, Anna Olejnik, Joanna Goscianska. Post-synthetic Modification and Engineering of Metal Nodes and Organic Ligands of MOFs for Catalytic Applications. 2023, 83-129.
    32. Gyanendra Kumar, Mohd Ehtesham, Satendra Kumar, Bachan Meena, Gobind Ji Rai, Dhanraj T. Masram. Metal–Organic Framework Sponges for Water Remediation. 2023, 247-261.
    33. Sowjanya Vallem, Joonho Bae. The Active Role of Conjugate Polymer Composites in Electrochemical Storage: A Themed Perspective on Polymer-MOF Nanocomposites for Metal-Ion Batteries. 2023, 211-228.
    34. Ibrahim M. Alarifi, Ramazan Asmatulu. Synthesis of hybrid composite materials. 2023, 23-43.
    35. Jaymin Parikh, Brij Mohan, Keyur Bhatt, Nihal Patel, Siddhant Patel, Amish Vyas, Krunal Modi. Effect of temperature on metal-organic frameworks chemical sensors detection properties. Microchemical Journal 2023, 184 , 108156.
    36. Leila Razavi, Heidar Raissi, Hassan Hashemzadeh, Farzaneh Farzad. Strategy to improve Cu-BTC metal-organic frameworks performance in removal of Rhodamine B: MD and WT-MtD simulations assessment. npj Clean Water 2022, 5 (1)
    37. Saman Houshiar, Zahra Rafiee, Majidreza Grami. Polymer/ZIF‐67 composite as an effective and recyclable nanocatalyst for Biginelli reaction. Applied Organometallic Chemistry 2022, 36 (9)
    38. Muhammad Idrees, Saima Batool, Jiwei Cao, Muhammad Sufyan Javed, Shufeng Xiong, Changyong Liu, Zhangwei Chen. 3D printed PC/SiOC@Zn hybrid composite as dendrite-free anode for Zn-Ion battery. Nano Energy 2022, 100 , 107505.
    39. Yicui Wei, Mengfan Wang, Wei Qi, Zhimin He. Flame-resistant bifunctional MOF-based sponges for effective separation of oil/water mixtures and enzyme-like degradation of organic pollutants. Process Safety and Environmental Protection 2022, 163 , 636-644.
    40. Muhammad Idrees, Saima Batool, Muhammad Sufyan Javed, Muhammad Aizaz Ud Din, Muhammad Imran, Zhangwei Chen. Preferred coordination of polymers at MOFs enables improved lithium-ion battery anode performance. Materials Chemistry Frontiers 2022, 6 (12) , 1690-1705.
    41. Debarati Mukherjee, Bart Van der Bruggen, Bishnupada Mandal. Advancements in visible light responsive MOF composites for photocatalytic decontamination of textile wastewater: A review. Chemosphere 2022, 295 , 133835.
    42. Siyi Rong, Pengcheng Su, Shizheng Chen, Miaomiao Jia, Wanbin Li. Sub-5 nm porous polymer decoration toward superhydrophobic MOFs with enhanced stability and processability. Chinese Chemical Letters 2022, 33 (4) , 2134-2138.
    43. Jiahao Li, Anruo Mao, Wei Yao, Haiyan Zhu, Dawei Wang. Iridium supported on porous polypyridine-oxadiazole as high-activity and recyclable catalyst for the borrowing hydrogen reaction. Green Chemistry 2022, 24 (6) , 2602-2612.
    44. Yuwei Gu, Julia Zhao, Jeremiah A. Johnson. Polymer Networks *. 2022, 1-52.
    45. Sanjam Chandna, Kunal Gogde, Ravneet Kaur, Varsha Sagar, Jayeeta Bhaumik. Nano-biosensors for Plant Biomass: Concept and Applications. 2022, 199-221.
    46. Ming-Ming Xu, Lin-Hua Xie, Jian-Rong Li. Metal–Organic Framework/Polymer Hybrid Materials. 2021, 72-97.
    47. Yousef Tamsilian, Zeinab Ansari-Asl, Ali Maghsoudian, Abdolreza Kazemi Abadshapoori, Amaia Agirre, Radmila Tomovska. Superhydrophobic ZIF8/PDMS-coated polyurethane nanocomposite sponge: Synthesis, characterization and evaluation of organic pollutants continuous separation. Journal of the Taiwan Institute of Chemical Engineers 2021, 125 , 204-214.
    48. Chaima Brahmi, Mahmoud Benltifa, Cyril Vaulot, Laure Michelin, Frédéric Dumur, Franck Millange, Michel Frigoli, Aissam Airoudj, Fabrice Morlet-Savary, Latifa Bousselmi, Jacques Lalevée. New hybrid MOF/polymer composites for the photodegradation of organic dyes. European Polymer Journal 2021, 154 , 110560.
    49. Gregory W. Peterson, Dennis T. Lee, Heather F. Barton, Thomas H. Epps, Gregory N. Parsons. Fibre-based composites from the integration of metal–organic frameworks and polymers. Nature Reviews Materials 2021, 6 (7) , 605-621.
    50. Fazheng Jin, Jinjin Liu, Yao Chen, Zhenjie Zhang. Tethering Flexible Polymers to Crystalline Porous Materials: A Win–Win Hybridization Approach. Angewandte Chemie 2021, 133 (26) , 14342-14355.
    51. Fazheng Jin, Jinjin Liu, Yao Chen, Zhenjie Zhang. Tethering Flexible Polymers to Crystalline Porous Materials: A Win–Win Hybridization Approach. Angewandte Chemie International Edition 2021, 60 (26) , 14222-14235.
    52. Sanjay Bisht, Sasikumar Balaguru, Sathish Kumar Ramachandran, Arthanareeswaran Gangasalam, Jihyang Kweon. Proton exchange composite membranes comprising SiO 2 , sulfonated SiO 2 , and metal–organic frameworks loaded in SPEEK polymer for fuel cell applications. Journal of Applied Polymer Science 2021, 138 (22)
    53. Syed Jalil Shah, Ruimeng Wang, Zhu Gao, Yaseen Muhammad, Hanzhuo Zhang, ZhengSheng Zhang, Zhe Chu, Zhongxing Zhao, Zhenxia Zhao. IL-assisted synthesis of defect-rich polyaniline/NH2-MIL-125 nanohybrids with strengthened interfacial contact for ultra-fast photocatalytic degradation of acetaldehyde under high humidity. Chemical Engineering Journal 2021, 411 , 128590.
    54. Vishnu Unnikrishnan, Omid Zabihi, Mojtaba Ahmadi, Quanxiang Li, Patrick Blanchard, Alper Kiziltas, Minoo Naebe. Metal–organic framework structure–property relationships for high-performance multifunctional polymer nanocomposite applications. Journal of Materials Chemistry A 2021, 9 (8) , 4348-4378.
    55. Vincent J. Pastore, Meghan G. Sullivan, Javid Rzayev, Timothy R. Cook. Postsynthetic polymer-ligand exchange hybridization in M-MOF-74 composites. Journal of Coordination Chemistry 2021, 74 (1-3) , 178-189.
    56. Sukhendu Mandal, Srinivasan Natarajan, Prabu Mani, Asha Pankajakshan. Post‐Synthetic Modification of Metal–Organic Frameworks Toward Applications. Advanced Functional Materials 2021, 31 (4)
    57. Nurul N. M. Ishak, N. N. M. Khiruddin, N. Nasri, T. B. S. A. Ravoof. Metal-Organic Frameworks (MOFs). 2021, 105-146.
    58. Shuliang Yang, Vikram V. Karve, Anita Justin, Ilia Kochetygov, Jordi Espín, Mehrdad Asgari, Olga Trukhina, Daniel T. Sun, Li Peng, Wendy L. Queen. Enhancing MOF performance through the introduction of polymer guests. Coordination Chemistry Reviews 2021, 427 , 213525.
    59. Surendra K. Yadav, G. Krishnamurthy Grandhi, Deepak P. Dubal, John C. de Mello, Michal Otyepka, Radek Zbořil, Roland A. Fischer, Kolleboyina Jayaramulu. Metal Halide Perovskite@Metal‐Organic Framework Hybrids: Synthesis, Design, Properties, and Applications. Small 2020, 16 (47)
    60. Huihui Li, Weiting Yang, Qinhe Pan. Integration of fluorescent probes into metal–organic frameworks for improved performances. RSC Advances 2020, 10 (56) , 33879-33893.
    61. Guohuan Huang, Danxia Xu, Zhimei Qin, Qun Liang, Chuanhui Xu, Baofeng Lin. Universal, controllable, large-scale and facile fabrication of nano-MOFs tightly-bonded on flexible substrate. Chemical Engineering Journal 2020, 395 , 125181.
    62. Mohamed E. Mahmoud, Asmaa K. Mohamed, Mohamed F. Amira, Seleim M. Seleim. Water-stable metal-organic framework/amine-modified silica/poly(piperazine-cresol) hybrids for efficient uptake of La(III) ions. Materials Chemistry and Physics 2020, 251 , 123107.
    63. Xin Hu, Xiaosong Hu, Qingxin Guan, Wei Li. Adjusting the active sites of Cu and ZnO by coordination effect of H 3 BTC and its influence on enhanced RWGS reaction. Sustainable Energy & Fuels 2020, 4 (6) , 2937-2949.
    64. Yuwei Gu, Julia Zhao, Jeremiah A. Johnson. Polymernetzwerke: Von Kunststoffen und Gelen zu porösen Gerüsten. Angewandte Chemie 2020, 132 (13) , 5054-5085.
    65. Yuwei Gu, Julia Zhao, Jeremiah A. Johnson. Polymer Networks: From Plastics and Gels to Porous Frameworks. Angewandte Chemie International Edition 2020, 59 (13) , 5022-5049.
    66. Bernhard V. K. J. Schmidt. Metal‐Organic Frameworks in Polymer Science: Polymerization Catalysis, Polymerization Environment, and Hybrid Materials. Macromolecular Rapid Communications 2020, 41 (1)
    67. Dimitrios Giliopoulos, Alexandra Zamboulis, Dimitrios Giannakoudakis, Dimitrios Bikiaris, Konstantinos Triantafyllidis. Polymer/Metal Organic Framework (MOF) Nanocomposites for Biomedical Applications. Molecules 2020, 25 (1) , 185.
    68. Zhouqing Xu, Jiwei Wang, Huijun Li, Yan Wang. Coating sponge with multifunctional and porous metal-organic framework for oil spill remediation. Chemical Engineering Journal 2019, 370 , 1181-1187.
    69. Mohamed H. Hassan, Mohamed H. Alkordi, Abdou Hassanien. Probing the conductivity of metal-organic framework-graphene nanocomposite. Materials Letters 2019, 246 , 13-16.
    70. Ross S. Forgan. The surface chemistry of metal–organic frameworks and their applications. Dalton Transactions 2019, 48 (25) , 9037-9042.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect